Method for selectively preparing evoglucosenone (LGO) and other anhydrosugars from biomass in polar aprotic solvents

Abstract

A method to produce 5-hydroxymethylfurfural (HMF) is described in which a reactant including cellulose, lignocellulose, or a combination thereof, in a reaction mixture of a polar, aprotic solvent and an acid is reacted for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the cellulose or lignocellulose present in the reactant is converted to HMF. The reaction mixture is initially substantially devoid of water. As the reaction proceeds, dehydration of intermediates causes the water concentration in the reaction mixture to rise to no more than about 2.0 wt % water.

What is claimed is: 
     
       1. A method to produce levoglucosenone (LGO), the method comprising:
 reacting a reactant comprising cellulose, lignocellulose, cellobiose, glucose, or a combination thereof, in a reaction mixture comprising a polar, aprotic solvent and an acid, for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the cellulose, lignocellulose, cellobiose, or glucose present in the reactant is converted to LGO. 
 
     
     
       2. The method of  claim 1 , wherein the acid is present in an amount to yield a hydrogen ion concentration in the reaction mixture of from about 5 mM to about 500 mM. 
     
     
       3. The method of  claim 1 , wherein the acid is present in an amount to yield a hydrogen ion concentration in the reaction mixture of from about 5 mM to about 100 mM. 
     
     
       4. The method of  claim 1 , wherein the acid is present in an amount to yield a hydrogen ion concentration in the reaction mixture of from about 5 mM to about 50 mM. 
     
     
       5. The method of  claim 1 , wherein the acid is a Brønsted-Lowry Acid. 
     
     
       6. The method of  claim 1 , wherein the acid is a mineral acid. 
     
     
       7. The method of  claim 1 , wherein the temperature is from about 80° C. to about 500° C. 
     
     
       8. The method of  claim 1 , wherein the temperature is from about 80° C. to about 400° C. 
     
     
       9. The method of  claim 1 , wherein the temperature is from about 80° C. to about 300° C. 
     
     
       10. The method of  claim 1 , wherein the temperature is from about 140° C. to about 250° C. 
     
     
       11. The method of  claim 1 , wherein the polar, aproptic solvent is selected from the group consisting of beta-, gamma-, and delta-lactones, hydrofurans, hydropyrans, dihydrolevoglucosenone, 6,8-dioxabicyclo-octane, and combinations thereof. 
     
     
       12. The method of  claim 1 , wherein the polar, aprotic solvent is selected from the group consisting of dichloromethane, tetrahydrofuran, ethylacetate, acetone, dimethylformamide, acetonitrile, dimethylsulfoxide, propylene carbonate, N-methyl-2-pyrrolidone, dihydrolevoglucosenone, 6,8-dioxabicyclo-octane, and hexamethylphosphoramide. 
     
     
       13. The method of  claim 1 , wherein the reaction mixture comprises no more than about 2.0 wt % water at any time during the reaction. 
     
     
       14. A method to produce levoglucosenone (LGO), the method comprising:
 reacting a reactant comprising cellulose, lignocellulose, cellobiose, glucose, or a combination thereof, in a reaction mixture comprising a polar, aprotic solvent and an acid, for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the cellulose or lignocellulose present in the reactant is converted to LGO; and 
 wherein the reaction mixture comprises no more than about 2.0 wt % water at any time during the reaction. 
 
     
     
       15. The method of  claim 14 , wherein the acid is present in an amount to yield a hydrogen ion concentration in the reaction mixture of from about 5 mM to about 500 mM. 
     
     
       16. The method of  claim 14 , wherein the acid is present in an amount to yield a hydrogen ion concentration in the reaction mixture of from about 5 mM to about 100 mM. 
     
     
       17. The method of  claim 14 , wherein the acid is present in an amount to yield a hydrogen ion concentration in the reaction mixture of from about 5 mM to about 50 mM. 
     
     
       18. The method of  claim 14 , wherein the acid is a Brønsted-Lowry acid. 
     
     
       19. The method of  claim 14 , wherein the acid is a mineral acid. 
     
     
       20. The method of  claim 14 , wherein the temperature is from about 80° C. to about 300° C. 
     
     
       21. The method of  claim 14 , wherein the temperature is from about 80° C. to about 500° C. 
     
     
       22. The method of  claim 14 , wherein the temperature is from about 80° C. to about 400° C. 
     
     
       23. The method of  claim 14 , wherein the temperature is from about 140° C. to about 250° C. 
     
     
       24. The method of  claim 14 , wherein the polar, aproptic solvent is selected from the group consisting of beta-, gamma-, and delta-lactones, hydrofurans, hydropyrans, dihydrolevoglucosenone, 6,8-dioxabicyclo-octane, and combinations thereof. 
     
     
       25. The method of  claim 14 , wherein the polar, aprotic solvent is selected from the group consisting of dichloromethane, tetrahydrofuran, ethylacetate, acetone, dimethylformamide, acetonitrile, dimethylsulfoxide, propylene carbonate, N-methyl-2-pyrrolidone, dihydrolevoglucosenone, 6,8-dioxabicyclo-octane, and hexamethylphosphoramide. 
     
     
       26. The method of  claim 14 , wherein the reaction mixture is initially substantially devoid of water. 
     
     
       27. The method of  claim 1 , wherein the reaction mixture is initially substantially devoid of water.